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Douglas G. Balmer
Dr. Dailey
Introduction: The purpose of this experiment was to separate a sample of benzoic acid, 2-
naphthol, and naphthalene of unknown proportions using a two-base extraction method. The
three components of the mixture will react differently to sodium bicarbonate and sodium
hydroxide because each of the bases’ conjugate acids has a different pKa. The pKa’s of benzoic
acid and 2-naphthol are 4.17 and 9.5, respectively, while naphthalene is a neutral compound.
Since benzoic acid is much more acidic than 2-naphthol, the weak base, sodium bicarbonate, will
be able to effectively remove benzoic acid’s acidic hydrogen. It will take the much stronger
base, sodium hydroxide, to remove the hydroxide hydrogen from 2-naphthol. Both of the
sodium salts formed from the base extractions will be soluble in water, while naphthalene will
only be soluble in the original solvent, diethyl ether. Introducing the two sodium salts to
hydrochloric acid will effectively replace the original proton benzoic acid and 2-naphthol lost.
In a chilled environment, both compounds will not be soluble in water, because the solubility of
benzoic acid and 2-naphthol in water at 25˚C is 0.34g/100mL and 0.074g/100mL, respectively.
They can be removed using vacuum filtration. After extraction and purification, the percent
recovery and percentage composition of the unknown sample will be able to be calculated.
The unknown sample may not be separated using melting points because both benzoic
acid and 2-naphthol have a melting point of 123˚C. The purity of the samples will be indicated
by their melting points ranges. The purer the sample, the narrower the melting point range.
Balmer 2
naphthalene (Table 1) was massed and the unknown number was recorded. The unknown
sample was dissolved in 30mL of diethyl ether in a 125mL Erlenmeyer flask. The solution was
transferred by funnel to a 125mL separatory funnel. The benzoic acid was extracted by adding
20mL of 10% aqueous sodium bicarbonate. The separatory funnel was swirled before inverting
to allow any carbon dioxide gas produced to dissipate. The inverted separatory funnel was
swirled with frequent venting until the fizzing carbon dioxide subsided. Afterwards, the inverted
separatory funnel was shaken with frequent venting until the fizzing carbon dioxide subsided.
The lower aqueous layer containing the benzoic acid was transferred to a labeled 125mL
Erlenmeyer flask. Any remaining benzoic acid in the organic layer was extracted with another
20mL of 10% aqueous sodium bicarbonate following the same procedure as detailed above. The
aqueous contents of both bicarbonate extractions were collected in the same 125mL Erlenmeyer
flask.
The 2-naphthol was extracted from the organic layer by adding 20mL of cold 10%
aqueous sodium hydroxide solution to the 125mL separatory funnel. The separatory funnel was
inverted and shaken with frequent venting. The lower aqueous layer was transferred to a second,
The ether solution was transferred to a labeled 50mL Erlenmeyer flask and 0.7g of
anhydrous sodium sulfate was added as a desiccant. The flask was corked to prevent
evaporation.
Balmer 3
O OH O O-
C C
OH O-
1 2 3 4 5
benzoic acid benzoate ion 2-naphthol 2-naphthoxide naphthalene
Unknown Sample
1,3,5
Dissovle unknown sample in ether.
Extract with aqueous sodium bicarbonate.
aqueous phase
3,5,ether
2, water, NaHCO3(aq)
1 5
3, water
Vaccuum filter the solution
and rinse with cold distilled
water.
FIGURE 1 Flow chart for the two-base extraction of benzoic acid, 2-naphthol, and naphthalene.
The aqueous bicarbonate extract containing the benzoic acid was acidified drop-wise
with 3M hydrochloric acid until a blue litmus paper test turned pink. The solution was swirled
while the acid was being added to allow the carbon dioxide gas formed to dissipate. The
aqueous sodium hydroxide extract containing the 2-naphthol was acidified as described above,
except the extract was chilled in an ice bath both prior and during the acidification process to
prevent the 2-naphtol from turning to an oil. Both of the acidified aqueous extracts were chilled
in an ice bath and the precipitates were individually isolated using a Büchner funnel with pre-
weighed filter paper. Both the benzoic acid and 2-naphthol were rinsed with cold distilled water
The ether solution containing the naphthalene was decanted into a pre-weighed, 100mL,
round-bottom flask. A rotary evaporator was used to pull off the ether. The naphthalene was
The mass of the benzoic acid and 2-naphthol were recorded after a week of air-drying.
Melting points were taken twice for all three chemicals on a Mel-Temp melting point apparatus.
Mel-Temp #13 was used for all of the melting points. At 80ºC the calibration curve was 3.5ºC
above the actual temperature, so 3.5ºC had to be subtracted from the measured melting points
near 80ºC. Above 100ºC the calibration curve was 4.0ºC above the actual temperature, so 4.0ºC
had to be subtracted from the measured melting points above 100ºC. All three samples were
Results and Observations: During the bicarbonate extraction, it was noted that the top ether layer
was a light tan color. The bottom aqueous layer was clear. It was also noted that there was
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hardly any carbon dioxide evolved. Very little pressure built up during the venting process.
After the second bicarbonate extraction, there were a few white crystals dispersed throughout the
Erlenmeyer flask. After the extraction with sodium hydroxide, the color of the layers changed.
This time the top ether layer was clear, and the bottom aqueous layer appeared a little tan and
cloudy.
It took 5ŌO drops of hydrochloric acid to acidify the aqueous bicarbonate solution to turn
a piece litmus paper pink. A precipitate formed on the top of the solution. After chilling the
solution in an ice bath, all of the precipitate dissolved, so another 30 drops of hydrochloric acid
needed to be added. The addition of 480 drops of hydrochloric acid formed a thick, milky-white
Three distinct products were isolated after extraction and a week of drying. The benzoic
acid was a very fine, white powder. The 2-naphthol was a fine, cream-colored powder. The
naphthalene was an off-white/tan powder with some clear crystals that smelled like mothballs.
%
Mass Melting Point
Sample Composition Color
(g) (ºC) corrected
(%)
mixture of white and
unknown # 131 1.93 -- -- cream powders,
flakes, and crystals
The total mass of the isolated products was 1.70g. Dividing by the mass of the original
unknown sample, 1.93g, yields a percent recovery of 88.1%. Dividing the mass of each of the
isolated products by the total mass of the isolated products yields the percent composition of the
recovered sample. The unknown sample consisted of 16% benzoic acid, 25% 2-naphthol, and
59% naphthalene.
Conclusions: The purpose of this experiment was to separate a sample of benzoic acid, 2-
naphthol, and naphthalene of unknown proportions. The data supports that the separation of all
three compounds was successful. The melting point ranges and colors of the products
correspond to the physical properties of benzoic acid, 2-naphthol, and naphthalene. The melting
points ranges show that the products are relatively pure since none of the ranges is greater than
1.8ºC.
The recovery of product from the original unknown sample was relatively high, 88.1%.
A small portion of product was lost during the first inverting of the separatory funnel when a few
drops of solution leaked out. Another small portion of product was lost during each separation
of the aqueous and ether layers. A few drops from the interface of the two layers were discarded
It was noted during the experiment that there was relatively little carbon dioxide
produced during the bicarbonate extraction compared to some of the other lab groups’ unknown
samples. A percent composition of 16% benzoic acid supports that there was relatively little
8) Fig. 2 shows a flow chart for the separation of benzoic acid, 4-nitroaniline, and N-(4-
O NH2 O
O
OH
O
-
N+ NH
N+
O
-
O
1 3 5
benzoic acid 4-nitroaniline N-(4-nitrophenyl)-benzamide
pKa=4.17 Solubility 0.08g/100mL H2O Solubility 0.08g/100mL H2O
Solubility 0.34g/100mL H2O
O NH3
O
O
-
N+
2 O
benzoate ion 4
4-nitroanilinium ion
Unknown Sample
1,3,5
Dissovle unknown sample in ether.
Extract with aqueous hydrochloric acid.
aqueous phase
1,5,ether
4, water, HCl (aq)
3 5
1, water
Vaccuum filter the solution
and rinse with cold distilled
water.
FIGURE 2 Flow chart for the two-base extraction of benzoic acid, 4-nitroaniline, and N-(4-
nitrophenyl)benzamide.
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11) The sequence of bases for the two-base extraction is critical to separating the benzoic
acid from the 2-naphthol. Benzoic acid has a pKa of 4.17, while 2-naphthol has a pKa of 9.5.
The conjugate acid of bicarbonate, H2CO3, has a pKa of 6.4. Since benzoic acid’s pKa is lower
than 6.4, it will deprotonate and become soluble in water, while 2-naphthol will remain in the
ether because it won’t deprotonate. If the sodium hydroxide were used first, both benzoic acid
and 2-naphthol would deprotonate and become soluble in water, because they both have a pKa